WO2021241245A1 - Phenolic resin composition sheet, phenolic resin composition sheet with release film, method for producing b-staged phenolic resin composite sheet, method for producing cured phenolic resin composite sheet, and method for producing carbonized phenolic resin composite sheet - Google Patents

Phenolic resin composition sheet, phenolic resin composition sheet with release film, method for producing b-staged phenolic resin composite sheet, method for producing cured phenolic resin composite sheet, and method for producing carbonized phenolic resin composite sheet Download PDF

Info

Publication number
WO2021241245A1
WO2021241245A1 PCT/JP2021/018179 JP2021018179W WO2021241245A1 WO 2021241245 A1 WO2021241245 A1 WO 2021241245A1 JP 2021018179 W JP2021018179 W JP 2021018179W WO 2021241245 A1 WO2021241245 A1 WO 2021241245A1
Authority
WO
WIPO (PCT)
Prior art keywords
sheet
phenol resin
resin composition
phenolic resin
composite sheet
Prior art date
Application number
PCT/JP2021/018179
Other languages
French (fr)
Japanese (ja)
Inventor
裕司 鈴木
Original Assignee
住友ベークライト株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2020094064A external-priority patent/JP2021187941A/en
Priority claimed from JP2020094058A external-priority patent/JP2021187940A/en
Priority claimed from JP2020094070A external-priority patent/JP2021187942A/en
Application filed by 住友ベークライト株式会社 filed Critical 住友ベークライト株式会社
Publication of WO2021241245A1 publication Critical patent/WO2021241245A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
    • B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to a phenol resin composition sheet, a phenol resin composition sheet with a release film using the phenol resin composition sheet, and a method for producing a B-staged phenol resin composite sheet using the phenol resin composition sheet, and curing.
  • the present invention relates to a method for producing a phenol formaldehyde composite sheet and a method for producing a carbonized phenol resin composite sheet.
  • Friction materials are used for the clutch to function properly, but are generally divided into “wet friction materials” that use oil and “dry friction materials” that do not use oil. The wet friction material can suppress an increase in frictional heat by using oil.
  • a papermaking body (fiber base material) is usually produced from fibers such as pulp and additives, and then the papermaking body is impregnated with a thermosetting resin, and the impregnated papermaking body is heat-treated.
  • the wet friction material thus produced is porous and has innumerable continuous pores on the surface and inside.
  • thermosetting resin used for producing the wet friction material a resol type phenol resin using an alcohol or a ketone organic solvent as a solvent is generally used.
  • the wet friction material deteriorates, the effect of transmitting the driving force decreases, so that the wet friction material is required to have high durability. Therefore, even in the thermosetting resin impregnated in the fiber base material, improvement in heat resistance and improvement in curability are required. Further, when the viscosity of the thermosetting resin is high, the impregnation property into the fiber base material is lowered and a desired wet friction material cannot be obtained, so that good impregnation property is required.
  • Patent Document 1 proposes a technique for improving the impregnation property into a fiber substrate by lowering the viscosity of a thermosetting resin. ..
  • the phenol resin that is liquid at room temperature and contains an organic solvent that is used by impregnating the fiber base material is disadvantageous from the viewpoint of environmental load and work environment because the organic solvent volatilizes in the manufacturing process of the friction material.
  • the present invention has been made in view of the above problems, and has a sheet-like phenolic resin composition having no problem of volatilization of an organic solvent, excellent handleability and workability, and good impregnation property with a fiber substrate. It provides things.
  • the present inventor uses a resin composition which is provided as a sheet-like product containing no organic solvent, which does not cause a problem of volatile solvent, has excellent handleability, and contains a specific compounding amount containing a specific component. It has been found that a phenolic resin composition that can realize good impregnation property with respect to the fiber base material at the time of melting and can be suitably used as a material for a wet friction material can be obtained, and has completed the present invention.
  • a layer of the phenol resin composition is arranged on at least one surface of the sheet-like substrate, and the layer of the phenol resin composition is heated to melt and liquefy the phenol resin composition and impregnate the substrate.
  • a phenolic resin composition sheet used in the process Resol type phenol resin and Polyvinyl butyral and Including The amount of the resole-type phenol resin is 50% by mass or more and 95% by mass or less with respect to the entire phenol resin composition sheet. It is like a B stage, A sheet-like phenolic resin composition sheet is provided.
  • a method for producing a cured phenol resin composite sheet including the above is provided.
  • a method for producing a carbonized phenol resin composite sheet is provided.
  • the sheet shape is excellent in handleability when used in the production of wet friction materials. Further, the phenolic resin composition of the present invention has a specific composition and thus has good impregnation property with respect to the fiber substrate when melted by heating.
  • the phenolic resin composition of the present embodiment is in the form of a sheet in a B stage state (semi-cured state), and is a resin material used as a binder for a fiber base material in the production of a wet friction material.
  • a layer of the phenol resin composition is arranged on at least one surface of a sheet-like base material which is a fiber base material (abstract body) of a wet friction material, and the phenol resin composition is prepared. It is used in the production of a wet friction material including a step of melting and liquefying the phenol resin composition by heating the layer and impregnating the sheet-like substrate with the liquid phenol resin composition.
  • the phenol resin composition sheet of the present embodiment is in the form of a sheet at room temperature, it is excellent in handleability and storability. Further, the phenol resin composition sheet of the present embodiment has an appropriate viscosity to penetrate into the fiber base material (abstract body) when it is melted by heating. Therefore, the inside of the fiber base material can be easily impregnated.
  • the phenol resin composition sheet of the present embodiment contains a resol type phenol resin and polyvinyl butyral, and the amount of the resol type phenol resin is 50% by mass or more and 95% by mass or less with respect to the entire phenol resin composition sheet. Is.
  • each component used in the phenol resin composition sheet of the present embodiment will be described.
  • the resol-type phenol resin used in the phenol resin composition sheet of the present embodiment is a phenol resin obtained by reacting a phenol resin with aldehydes in the presence of a basic catalyst.
  • phenols used for the synthesis of the resole-type phenol resin include phenols; cresols such as o-cresol, m-cresol, p-cresol; o-ethylphenol, m-ethylphenol, p-ethylphenol and the like.
  • Aldehydes used for the synthesis of resole-type phenolic resins include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glioxal, n-butylaldehyde, and capro. Examples thereof include aldehyde, allyl aldehyde, benzaldehyde, croton aldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde and the like.
  • Basic catalysts used for the synthesis of resole-type phenolic resins include, for example, hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, calcium hydroxide; sodium carbonate, calcium carbonate. Carbonates such as; oxides such as lime; sulfites such as sodium sulfite; phosphates such as sodium phosphate; ammonia, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, hexamethylenetetramine, pyridine and the like. Examples include amines.
  • Water is generally used as the reaction solvent for synthesizing the resole-type phenol resin, but an organic solvent may be used.
  • organic solvent include alcohols, ketones, aromatics and the like.
  • alcohols include methanol, ethanol, propyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, glycerin and the like.
  • ketones include acetone, methyl ethyl ketone and the like.
  • aromatics include toluene, xylene and the like.
  • the content of the resole-type phenol resin is 50% by mass or more and 95% by mass or less, preferably 60% by mass or more and 95% by mass, based on the entire phenol resin composition sheet. It is 0% by mass or less, and more preferably 70% by mass or more and 90% by mass or less.
  • the obtained phenol resin composition sheet has sufficient heat resistance and durability for use as a wet friction material. Further, by setting the content of the resol type phenol resin to the above lower limit value or more, the residual carbon content of the obtained phenol resin composition sheet can be maintained high, and therefore, the wet friction material produced by using the sheet can be used. Excellent in heat resistance and mechanical strength.
  • Polyvinyl butyral used in the phenol resin composition sheet of the present embodiment has an action of solidifying a liquid resol type phenol resin and acts as a sheet forming material. Further, by using polyvinyl butyral, flexibility can be imparted to the obtained phenol resin composition sheet. Therefore, the phenolic resin composition sheet of the present embodiment can be cut to a desired size or punched into a desired shape according to a desired application.
  • Polyvinyl butyral is a resin obtained by converting polyvinyl alcohol to butyral with an aldehyde in the presence of an acid catalyst.
  • the weight average molecular weight of the polyvinyl butyral from the viewpoint of handling properties, preferably 1.0 ⁇ 10 4 ⁇ 1.0 ⁇ 10 6, more preferably 2.0 ⁇ 10 4 ⁇ 5.0 ⁇ 10 5 Yes, more preferably 3.0 ⁇ 10 4 to 2.0 ⁇ 10 5 .
  • the weight average molecular weight is based on polystyrene conversion measured by gel permeation chromatography (GPC).
  • the degree of polymerization of polyvinyl butyral is preferably in the range of 200 to 3000.
  • the degree of polymerization of polyvinyl butyral is preferably in the range of 200 to 3000.
  • the content of polyvinyl butyral is, for example, 2% by mass or more and 50% by mass or less, preferably 5% by mass or more and 40% by mass or less, and more preferably 10% by mass or more, based on the entire phenol resin composition. It is 30% by mass or less.
  • the viscosity of the obtained phenol resin composition sheet at the time of melting can be suppressed to a low level, and thus the impregnation property to the fiber substrate can be improved.
  • the obtained phenol resin composition sheet has sufficient heat resistance and durability for use as a wet friction material.
  • the residual carbon content of the obtained phenol resin composition sheet can be maintained high, and therefore, the wet friction material produced by using the sheet has heat resistance. Excellent in properties and mechanical strength.
  • the phenolic resin composition sheet of the present embodiment may further contain resorcins.
  • resorcins include methyl resorcins such as resorcin, 2-methylresorcin, 5-methylresorcin, and 2,5-dimethylresorcin, 4-ethylresorcin, 4-chlororesorcin, 2-nitroresorcin, and 4-bromo.
  • Resorcin, 4-n-hexyl resorcin and the like can be mentioned. These may be used alone or in combination of two or more. Above all, it is preferable to use resorcin or methylresorcin from the viewpoint of manufacturing cost and sheet formability.
  • the phenolic resin composition sheet of the present embodiment contains elastomers such as nitrile butadiene rubber and styrene butadiene rubber, surfactants, flame retardants, antioxidants, and colorants as long as the effects of the present invention are not impaired.
  • Additives such as silane coupling agents may be included.
  • phenol resin composition sheet Preparation of phenol resin composition sheet
  • a liquid or varnish-like phenol resin composition obtained by dissolving the above components in an organic solvent is applied to a base sheet or the like, and the organic solvent is removed by heat treatment. It is produced by forming it into a sheet and then heat-treating it to a B stage state (semi-cured state).
  • the thickness of the phenol resin composition sheet is preferably 5 ⁇ m or more and 200 ⁇ m or less.
  • the phenol resin composition sheet can be in the form of a tape having a width of 10 mm or more and 100 mm or less, or a sheet having a width of 10 cm or more and 200 cm or less.
  • organic solvent used in the varnish-like phenol resin composition examples include alcohol-based organic solvents such as methanol, ethanol, isopropanol and butanol, ketone-based organic solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and aromatics such as toluene and ethyl benzene.
  • alcohol-based organic solvents such as methanol, ethanol, isopropanol and butanol
  • ketone-based organic solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone
  • aromatics such as toluene and ethyl benzene.
  • hydrocarbon solvents and mixtures thereof Of these, methanol is preferably used.
  • the varnish-like phenol resin composition is prepared by kneading the above components in an organic solvent.
  • the kneading can be carried out by appropriately combining a normal stirrer, a three-roll, a disperser such as a ball mill.
  • the varnish-like phenol resin composition is applied to the base sheet and dried by heating to remove the organic solvent to form the phenol resin composition layer. It is done by.
  • the heat-drying condition may be any condition as long as the organic solvent used is volatilized, and is performed, for example, at a temperature of 50 ° C. to 150 ° C. for a time of 1 minute to 90 minutes.
  • the phenolic resin composition layer obtained as described above is further heat-treated to be in a semi-cured (B stage) state.
  • a condition of a temperature of 100 to 200 ° C. and a time of 1 minute to 60 minutes can be used.
  • the sheet-like substrate is not particularly limited as long as it can withstand the above-mentioned heat-drying conditions, and is, for example, a polyester-based film, a polypropylene-based film, a polyimide-based film, a polyamide-based film, a polysulfone-based film, or a polyetherketone-based film. Film or the like is used.
  • the surface of these sheet-like substrates may be treated with a mold release agent.
  • the base sheet may be removed after the phenolic resin composition layer is formed. Further, the phenol resin composition sheet thus obtained may be provided as a phenol resin composition sheet with a release film, in which a release film is provided on a surface opposite to the surface facing the base sheet. good.
  • the release film the same one as the base sheet can be used.
  • the minimum melt viscosity of the phenolic resin composition sheet of the present embodiment is, for example, 5000 Pa ⁇ s or less, preferably 4000 Pa ⁇ s or less, and more preferably 3000 Pa ⁇ s or less.
  • the minimum melt viscosity can be adjusted by setting the type of phenol resin used and the blending amount of polyvinyl butyral within the above ranges.
  • the lower limit of the minimum melt viscosity of the phenolic resin composition sheet is, for example, 200 Pa ⁇ s or more. If the minimum melt viscosity is in the above range, the inside of the fiber base material can be easily impregnated, and the impregnation property can be the same as when the liquid impregnating phenol resin composition is used at room temperature.
  • the minimum melt viscosity of the phenol resin composition sheet means the minimum viscosity exhibited by the phenol resin composition when the phenol resin composition sheet is melted by heating. Specifically, when the phenol resin composition sheet is heated at a constant temperature rise rate to melt the resin, the melt viscosity decreases with increasing temperature in the initial stage, and then, when the temperature exceeds a certain level, the melt viscosity increases with temperature increase. To rise.
  • the minimum melt viscosity means the melt viscosity at such a minimum point.
  • the minimum melt viscosity of the resin composition layer can be measured by the dynamic viscoelastic method.
  • the phenolic resin composition sheet of the present embodiment has a residual carbon content of, for example, 30% by mass or more, preferably 35% by mass or more, and more preferably 40% by mass or more.
  • the upper limit of the residual carbon content of the phenol resin composition sheet is not particularly limited, but is, for example, 80% by mass or less.
  • the residual coal ratio of the phenol resin composition sheet is the residual carbon ratio at a temperature of 800 ° C. measured according to JIS K6910.
  • the phenol resin composition sheet of the present embodiment has a residual carbon content of 30% by mass or more by containing the above-mentioned resole-type phenol resin in the above-mentioned blending amount.
  • Such a phenol resin composition sheet has excellent heat resistance, and therefore the wet friction material produced by using the same has excellent heat resistance.
  • the phenol resin composition sheet of the present embodiment is used as a wet friction material produced by curing and firing (carbonizing) a fiber base material (precursor sheet) impregnated with the phenol resin composition.
  • the fiber base material (precursor sheet) impregnated with the phenol resin composition is composed of a fiber base material and a B-stage-like phenol resin composition impregnated with the fiber base material.
  • This B-staged phenol resin composite sheet is produced by the following steps.
  • A2) A step of laminating the phenol resin composition sheet of the present embodiment on at least one surface of the sheet-like substrate;
  • A3) A step of heating the phenol resin composition sheet to melt and liquefy the phenol resin composition sheet and impregnate the sheet-like substrate with the liquefied phenol resin composition, a resin-impregnated sheet (B-staged phenol).
  • a process of producing a resin composite sheet ).
  • the step of preparing the sheet-shaped base material in the above step (A1) is a step of making a sheet-shaped base material by making paper from carbon fibers or aramid fibers.
  • a commercially available product may be used as the sheet-like substrate.
  • the sheet-like base material is a fiber base material (paper machine) to be a wet friction material, and an additive such as a friction modifier for controlling friction may be added to the fiber base material (papermaking body).
  • the phenol resin composition sheet of the present embodiment is laminated on one surface or both sides of the sheet-like substrate prepared in (A1), and then melted by heating to form a sheet-like group. This is the process of impregnating the material. Since the phenol resin composition sheet of the present embodiment is in the form of a sheet, the step of laminating on the sheet-like substrate is easy, and the step of impregnating the sheet-like substrate with the phenol resin composition is carried out by using a liquid phenol resin. It can be carried out relatively easily as compared with the method of impregnating the fiber base material.
  • the step of heating the sheet-like base material on which the phenol resin composition sheet is laminated is preferably carried out under pressure.
  • the molten phenol resin composition is easily impregnated into the sheet-like substrate.
  • the heating and pressurizing conditions for example, a temperature of 60 ° C. to 150 ° C. and a pressure of 1 MPa to 50 MPa are used.
  • the phenol resin composition sheet of the present embodiment contains almost or no organic solvent, the solvent does not volatilize during heating. Therefore, a good working environment is guaranteed. Further, since the step of arranging the sheet-shaped phenol resin composition on the fiber base material can be carried out in one step, the work efficiency is improved.
  • the phenolic resin composition sheet of the present embodiment may be cut out so as to match the dimensions and shape of the sheet-like substrate before being placed on the sheet-like substrate. Further, as the phenol resin composition sheet of the present embodiment, only one sheet may be arranged on the sheet-like substrate, or a plurality of two or more sheets may be arranged, if desired.
  • the fiber base material impregnated with the phenol resin composition is provided as a cured phenol resin composite sheet composed of the fiber base material and the cured phenol resin composition.
  • the cured phenol resin composite sheet can be produced by the following steps. (A4) A step of heat-treating the B-staged phenolic resin composite sheet obtained in (A3) above to completely cure the B-staged phenolic resin composition.
  • the step of completely curing the phenol resin composition in the above step (A4) can be carried out, for example, by heating at a temperature of 100 ° C. to 200 ° C. for 3 minutes to 3 hours.
  • the fiber base material impregnated with the phenol resin composition is provided as a carbonized phenol resin composite sheet composed of the fiber base material and the carbonized phenol resin composition.
  • the carbonized phenol resin composite sheet can be produced by the following steps. (A5) A step of heat-treating the cured phenol resin composite sheet obtained in (A4) above to carbonize the cured phenol resin composition.
  • the step of carbonizing the phenolic resin composition in the above step (A5) can be carried out, for example, by heating at a temperature of 350 ° C. to 2000 ° C. for 1 hour to 8 hours.
  • the carbonized phenol resin composite sheet of this embodiment can be used as a wet friction material.
  • Example 2 The same method as in Example 1 except that the polyvinyl butyral resin (manufactured by Sekisui Chemical Co., Ltd., Eslek BM-1) in Example 1 was changed to the polyvinyl butyral resin Eslek BH-3 (calculated molecular weight 110,000) manufactured by Sekisui Chemical Co., Ltd. was used to obtain a phenol resin composition sheet 2 containing 75% of resole-type phenol resin and 20% of polyvinyl butyral.
  • the polyvinyl butyral resin manufactured by Sekisui Chemical Co., Ltd., Eslek BM-1
  • Eslek BH-3 calculated molecular weight 110,000
  • the resin sheet of the example had good impregnation property with respect to the fiber base material and also had excellent mechanical strength after heat treatment of the cured product, and was a material that could be suitably used as a friction material.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

A phenolic resin composition sheet which is used for a step wherein a layer of a phenolic resin composition is arranged on at least one surface of a sheet-like base material and the phenolic resin composition is melted and liquefied by heating the layer of the phenolic resin composition, thereby having the base material impregnated with the phenolic resin composition. This phenolic resin composition sheet contains a resol type phenolic resin and a polyvinyl butyral; the amount of the resol type phenolic resin is from 50% by mass to 95% by mass relative to the entirety of the phenolic resin composition sheet; and this phenolic resin composition sheet is in a B-stage state, while being in the form of a sheet.

Description

フェノール樹脂組成物シート、剥離フィルム付フェノール樹脂組成物シート、Ｂステージ化フェノール樹脂複合シートの製造方法、硬化フェノール樹脂複合シートの製造方法、および炭素化フェノール樹脂複合シートの製造方法Phenol resin composition sheet, phenol resin composition sheet with release film, B-staged phenol resin composite sheet manufacturing method, cured phenol resin composite sheet manufacturing method, and carbonized phenol resin composite sheet manufacturing method.
　本発明は、フェノール樹脂組成物シート、当該フェノール樹脂組成物シートを用いた剥離フィルム付フェノール樹脂組成物シート、当該フェノール樹脂組成物シートを用いた、Ｂステージ化フェノール樹脂複合シートの製造方法、硬化フェノール樹脂複合シートの製造方法、および炭素化フェノール樹脂複合シートの製造方法に関する。 INDUSTRIAL APPLICABILITY The present invention relates to a phenol resin composition sheet, a phenol resin composition sheet with a release film using the phenol resin composition sheet, and a method for producing a B-staged phenol resin composite sheet using the phenol resin composition sheet, and curing. The present invention relates to a method for producing a phenol formaldehyde composite sheet and a method for producing a carbonized phenol resin composite sheet.
　オートマチック車等の自動変速機には、エンジンとトランスミッション（変速機）の間に取り付けられ、発進、停止、変速時にエンジンの力をトランスミッションに伝えたり遮断したりするために、クラッチが使用されている。摩擦材は、当該クラッチが適切に機能するために用いられるが、一般に、オイルを使用する「湿式摩擦材」と、オイルを使用しない「乾式摩擦材」とに分けられる。湿式摩擦材は、オイルを使用することにより、摩擦熱の上昇を抑制することができる。 In automatic transmissions such as automatic cars, a clutch is installed between the engine and the transmission (transmission) to transmit or shut off the power of the engine to the transmission when starting, stopping, or shifting. .. Friction materials are used for the clutch to function properly, but are generally divided into "wet friction materials" that use oil and "dry friction materials" that do not use oil. The wet friction material can suppress an increase in frictional heat by using oil.
　湿式摩擦材は、通常、パルプなどの繊維および添加剤を原料として抄紙体（繊維基材）を製造し、次いで、抄紙体に熱硬化性樹脂を含浸させて、含浸後の抄紙体を加熱処理することによって製造される。このようにして製造された湿式摩擦材は多孔質であり、表面及び内部に無数の連続的な気孔を有している。 In a wet friction material, a papermaking body (fiber base material) is usually produced from fibers such as pulp and additives, and then the papermaking body is impregnated with a thermosetting resin, and the impregnated papermaking body is heat-treated. Manufactured by The wet friction material thus produced is porous and has innumerable continuous pores on the surface and inside.
　湿式摩擦材の製造に用いられる熱硬化性樹脂としては、アルコールやケトン系有機溶剤を溶媒としたレゾール型フェノール樹脂が一般的に用いられている。湿式摩擦材が劣化すると駆動力の伝達効力が低下するため、湿式摩擦材には高い耐久性が要求される。そのため、繊維基材に含浸させる熱硬化性樹脂においても、耐熱性の向上や硬化性の改善が求められる。また、熱硬化性樹脂の粘度が高い場合には繊維基材への含浸性が低下して所望の湿式摩擦材が得られないため、良好な含浸性が求められる。これらの課題を改善するための種々の提案がなされており、たとえば、特許文献１では、熱硬化性樹脂を低粘度化することにより繊維基材への含浸性を改善する技術が提案されている。 As the thermosetting resin used for producing the wet friction material, a resol type phenol resin using an alcohol or a ketone organic solvent as a solvent is generally used. When the wet friction material deteriorates, the effect of transmitting the driving force decreases, so that the wet friction material is required to have high durability. Therefore, even in the thermosetting resin impregnated in the fiber base material, improvement in heat resistance and improvement in curability are required. Further, when the viscosity of the thermosetting resin is high, the impregnation property into the fiber base material is lowered and a desired wet friction material cannot be obtained, so that good impregnation property is required. Various proposals have been made to improve these problems. For example, Patent Document 1 proposes a technique for improving the impregnation property into a fiber substrate by lowering the viscosity of a thermosetting resin. ..
特開２０１５－２３２０６２号公報Japanese Unexamined Patent Publication No. 2015-232062
　しかしながら繊維基材に含浸させて使用する有機溶剤を含む室温で液状のフェノール樹脂は、摩擦材の製造工程において有機溶剤が揮発するため、環境負荷や作業環境の観点から不利であった。 However, the phenol resin that is liquid at room temperature and contains an organic solvent that is used by impregnating the fiber base material is disadvantageous from the viewpoint of environmental load and work environment because the organic solvent volatilizes in the manufacturing process of the friction material.
　本発明は、上記課題に鑑みてなされたものであり、有機溶剤の揮発の問題がなく、取り扱い性や作業性が優れるとともに、繊維基材に対する含浸性が良好である、シート状のフェノール樹脂組成物を提供するものである。 The present invention has been made in view of the above problems, and has a sheet-like phenolic resin composition having no problem of volatilization of an organic solvent, excellent handleability and workability, and good impregnation property with a fiber substrate. It provides things.
　本発明者は、有機溶剤を含まないシート状物として提供することにより、揮発溶剤の問題が生じず、取り扱い性に優れ、特定の成分を含む特定の配合量で含む樹脂組成物を用いることにより溶融時の繊維基材に対する良好な含浸性を実現でき、よって湿式摩擦材の材料として好適に使用できるフェノール樹脂組成物が得られることを見出し、本発明を完成するに至った。 The present inventor uses a resin composition which is provided as a sheet-like product containing no organic solvent, which does not cause a problem of volatile solvent, has excellent handleability, and contains a specific compounding amount containing a specific component. It has been found that a phenolic resin composition that can realize good impregnation property with respect to the fiber base material at the time of melting and can be suitably used as a material for a wet friction material can be obtained, and has completed the present invention.
　本発明によれば、
シート状基材の少なくとも一表面上にフェノール樹脂組成物の層を配置し、前記フェノール樹脂組成物の層を加熱することにより前記フェノール樹脂組成物を溶融して液状化し、前記基材に含浸させる工程に用いられる、フェノール樹脂組成物シートであって、
　レゾール型フェノール樹脂と、
　ポリビニルブチラールと、
　を含み、
　　前記レゾール型フェノール樹脂が、当該フェノール樹脂組成物シート全体に対して、５０質量％以上９５質量％以下の量であり、
　Ｂステージ状であり、
　シート状である、フェノール樹脂組成物シートが提供される。 According to the present invention
A layer of the phenol resin composition is arranged on at least one surface of the sheet-like substrate, and the layer of the phenol resin composition is heated to melt and liquefy the phenol resin composition and impregnate the substrate. A phenolic resin composition sheet used in the process.
Resol type phenol resin and
Polyvinyl butyral and
Including
The amount of the resole-type phenol resin is 50% by mass or more and 95% by mass or less with respect to the entire phenol resin composition sheet.
It is like a B stage,
A sheet-like phenolic resin composition sheet is provided.
　また本発明によれば、
　シート状基材の少なくとも一方の面上に、上記フェノール樹脂組成物シートを積層する工程と、
　前記フェノール樹脂組成物シートを加熱することにより前記フェノール樹脂組成物シートを溶融して液状化し、前記液状化フェノール樹脂組成物を前記シート状基材に含浸させて、Ｂステージ化フェノール樹脂複合シートを得る工程を含む、
　Ｂステージ化フェノール樹脂複合シートの製造方法が提供される。 Further, according to the present invention.
The step of laminating the above-mentioned phenol resin composition sheet on at least one surface of the sheet-like substrate, and
By heating the phenol resin composition sheet, the phenol resin composition sheet is melted and liquefied, and the sheet-like substrate is impregnated with the liquefied phenol resin composition to obtain a B-staged phenol resin composite sheet. Including the process of obtaining,
A method for producing a B-staged phenolic resin composite sheet is provided.
　また本発明によれば、
　シート状基材の少なくとも一方の面上に、上記フェノール樹脂組成物シートを積層する工程と、
　前記フェノール樹脂組成物シートを加熱することにより前記フェノール樹脂組成物シートを溶融して液状化し、前記液状化フェノール樹脂組成物を前記シート状基材に含浸させて、Ｂステージ化フェノール樹脂複合シートを得る工程と、
　前記Ｂステージ化フェノール樹脂複合シートを加熱して、前記フェノール樹脂組成物を完全硬化させて、硬化フェノール樹脂複合シートを得る工程と、
　を含む、硬化フェノール樹脂複合シートの製造方法が提供される。 Further, according to the present invention.
The step of laminating the above-mentioned phenol resin composition sheet on at least one surface of the sheet-like substrate, and
By heating the phenol resin composition sheet, the phenol resin composition sheet is melted and liquefied, and the sheet-like substrate is impregnated with the liquefied phenol resin composition to obtain a B-staged phenol resin composite sheet. The process of obtaining and
A step of heating the B-staged phenol resin composite sheet to completely cure the phenol resin composition to obtain a cured phenol resin composite sheet.
A method for producing a cured phenol resin composite sheet including the above is provided.
　また本発明によれば、
　シート状基材の少なくとも一方の面上に、上記フェノール樹脂組成物シートを積層する工程と、
　前記フェノール樹脂組成物シートを加熱することにより前記フェノール樹脂組成物シートを溶融して液状化し、前記液状化フェノール樹脂組成物を前記シート状基材に含浸させて、Ｂステージ化フェノール樹脂複合シートを得る工程と、
　前記Ｂステージ化フェノール樹脂複合シートを加熱して、前記フェノール樹脂組成物を完全硬化させて、硬化フェノール樹脂複合シートを得る工程と、
　前記硬化フェノール樹脂複合シートを加熱して、前記フェノール樹脂組成物を炭素化して、炭素化フェノール樹脂複合シートを得る工程と、
　を含む、炭素化フェノール樹脂複合シートの製造方法が提供される。 Further, according to the present invention.
The step of laminating the above-mentioned phenol resin composition sheet on at least one surface of the sheet-like substrate, and
By heating the phenol resin composition sheet, the phenol resin composition sheet is melted and liquefied, and the sheet-like substrate is impregnated with the liquefied phenol resin composition to obtain a B-staged phenol resin composite sheet. The process of obtaining and
A step of heating the B-staged phenol resin composite sheet to completely cure the phenol resin composition to obtain a cured phenol resin composite sheet.
A step of heating the cured phenol resin composite sheet to carbonize the phenol resin composition to obtain a carbonized phenol resin composite sheet.
A method for producing a carbonized phenol resin composite sheet is provided.
　本発明のフェノール樹脂組成物によれば、シート形状であることにより、湿式摩擦材の製造において使用する際の取り扱い性に優れる。また本発明のフェノール樹脂組成物は、特定の組成を有することにより、加熱により溶融された際に、繊維基材に対する良好な含浸性を備える。 According to the phenol resin composition of the present invention, the sheet shape is excellent in handleability when used in the production of wet friction materials. Further, the phenolic resin composition of the present invention has a specific composition and thus has good impregnation property with respect to the fiber substrate when melted by heating.
　以下、本発明の実施の形態について説明する。
　本実施形態のフェノール樹脂組成物は、Ｂステージ状態（半硬化状態）のシート状であり、湿式摩擦材を製造において繊維基材の結着剤として用いられる樹脂材料である。本実施形態のフェノール樹脂組成物シートは、湿式摩擦材の繊維基材（抄造体）であるシート状基材の少なくとも一表面上にフェノール樹脂組成物の層を配置し、このフェノール樹脂組成物の層を加熱することによりフェノール樹脂組成物を溶融して液状化し、シート状基材にこの液状フェノール樹脂組成物を含浸させる工程を含む湿式摩擦材の製造に用いられる。 Hereinafter, embodiments of the present invention will be described.
The phenolic resin composition of the present embodiment is in the form of a sheet in a B stage state (semi-cured state), and is a resin material used as a binder for a fiber base material in the production of a wet friction material. In the phenol resin composition sheet of the present embodiment, a layer of the phenol resin composition is arranged on at least one surface of a sheet-like base material which is a fiber base material (abstract body) of a wet friction material, and the phenol resin composition is prepared. It is used in the production of a wet friction material including a step of melting and liquefying the phenol resin composition by heating the layer and impregnating the sheet-like substrate with the liquid phenol resin composition.
　本実施形態のフェノール樹脂組成物シートは、室温でシート状であるため、取り扱い性や保管性に優れる。また本実施形態のフェノール樹脂組成物シートは、加熱により溶融された際に、繊維基材（抄造体）の内部に浸透するのに適切な粘度となる。したがって繊維基材内部まで容易に含浸させることができる。本実施形態のフェノール樹脂組成物シートは、レゾール型フェノール樹脂と、ポリビニルブチラールとを含み、レゾール型フェノール樹脂は、当該フェノール樹脂組成物シート全体に対して、５０質量％以上９５質量％以下の量である。以下に、本実施形態のフェノール樹脂組成物シートに用いられる各成分について説明する。 Since the phenol resin composition sheet of the present embodiment is in the form of a sheet at room temperature, it is excellent in handleability and storability. Further, the phenol resin composition sheet of the present embodiment has an appropriate viscosity to penetrate into the fiber base material (abstract body) when it is melted by heating. Therefore, the inside of the fiber base material can be easily impregnated. The phenol resin composition sheet of the present embodiment contains a resol type phenol resin and polyvinyl butyral, and the amount of the resol type phenol resin is 50% by mass or more and 95% by mass or less with respect to the entire phenol resin composition sheet. Is. Hereinafter, each component used in the phenol resin composition sheet of the present embodiment will be described.
（レゾール型フェノール樹脂）
　本実施形態のフェノール樹脂組成物シートに用いられるレゾール型フェノール樹脂は、フェノール樹脂とアルデヒド類とを、塩基性触媒の存在下で反応させて得られるフェノール樹脂である。 (Resol type phenol resin)
The resol-type phenol resin used in the phenol resin composition sheet of the present embodiment is a phenol resin obtained by reacting a phenol resin with aldehydes in the presence of a basic catalyst.
　レゾール型フェノール樹脂の合成のために使用されるフェノール類としては、フェノール；ｏ－クレゾール、ｍ－クレゾール、ｐ－クレゾール等のクレゾール類；ｏ－エチルフェノール、ｍ－エチルフェノール、ｐ－エチルフェノール等のエチルフェノール類；イソプロピルフェノール、ブチルフェノール、ｐ－ｔｅｒｔ－ブチルフェノール等のブチルフェノール類；ｐ－ｔｅｒｔ－アミルフェノール、ｐ－オクチルフェノール、ｐ－ノニルフェノール、ｐ－クミルフェノール等のアルキルフェノール類；フルオロフェノール、クロロフェノール、ブロモフェノール、ヨードフェノール等のハロゲン化フェノール類；ｐ－フェニルフェノール、アミノフェノール、ニトロフェノール、ジニトロフェノール、トリニトロフェノール等の１価フェノール置換体：１－ナフトール、２－ナフトール等の１価のフェノール類；およびレゾルシン、アルキルレゾルシン、ピロガロール、カテコール、アルキルカテコール、ハイドロキノン、アルキルハイドロキノン、フロログルシン、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、ジヒドロキシナフタリン等の多価フェノール類等が挙げられる。これらは、単独でかまたは２種以上混合して使用できる。 Examples of the phenols used for the synthesis of the resole-type phenol resin include phenols; cresols such as o-cresol, m-cresol, p-cresol; o-ethylphenol, m-ethylphenol, p-ethylphenol and the like. Ethylphenols; butylphenols such as isopropylphenol, butylphenol, p-tert-butylphenol; alkylphenols such as p-tert-amylphenol, p-octylphenol, p-nonylphenol, p-cumylphenol; fluorophenols, chlorophenols. , Bromophenol, iodophenol and other halogenated phenols; monovalent phenol substituents such as p-phenylphenol, aminophenol, nitrophenol, dinitrophenol and trinitrophenol: monovalent such as 1-naphthol and 2-naphthol. Phenols; and polyhydric phenols such as resorcin, alkylresorcin, pyrogallol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, fluoroglucolcin, bisphenol A, bisphenol F, bisphenol S, dihydroxynaphthalin and the like. These can be used alone or in admixture of two or more.
　レゾール型フェノール樹脂の合成のために使用されるアルデヒド類としては、ホルムアルデヒド、パラホルムアルデヒド、トリオキサン、アセトアルデヒド、プロピオンアルデヒド、ポリオキシメチレン、クロラール、ヘキサメチレンテトラミン、フルフラール、グリオキザール、ｎ－ブチルアルデヒド、カプロアルデヒド、アリルアルデヒド、ベンズアルデヒド、クロトンアルデヒド、アクロレイン、テトラオキシメチレン、フェニルアセトアルデヒド、ｏ－トルアルデヒド、サリチルアルデヒド等が挙げられる。これらは、単独で使用してもよいし、２種類以上組み合わせて使用してもよい。また、これらのアルデヒド類の前駆体あるいはこれらのアルデヒド類の溶液を使用することもできる。中でも、製造コストの観点から、ホルムアルデヒド水溶液を使用することが好ましい。 Aldehydes used for the synthesis of resole-type phenolic resins include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glioxal, n-butylaldehyde, and capro. Examples thereof include aldehyde, allyl aldehyde, benzaldehyde, croton aldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde and the like. These may be used alone or in combination of two or more. Further, precursors of these aldehydes or solutions of these aldehydes can also be used. Above all, it is preferable to use an aqueous formaldehyde solution from the viewpoint of manufacturing cost.
　レゾール型フェノール樹脂の合成のために使用される塩基性触媒としては、例えば、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム等のアルカリ金属もしくはアルカリ土類金属の水酸化物；炭酸ナトリウム、炭酸カルシウム等の炭酸塩；石灰等の酸化物；亜硫酸ナトリウム等の亜硫酸塩；リン酸ナトリウム等のリン酸塩；アンモニア、トリメチルアミン、トリエチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ヘキサメチレンテトラミン、ピリジン等のアミン類等が挙げられる。 Basic catalysts used for the synthesis of resole-type phenolic resins include, for example, hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, calcium hydroxide; sodium carbonate, calcium carbonate. Carbonates such as; oxides such as lime; sulfites such as sodium sulfite; phosphates such as sodium phosphate; ammonia, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, hexamethylenetetramine, pyridine and the like. Examples include amines.
　レゾール型フェノール樹脂の合成のために使用される反応溶媒としては、水が一般的であるが、有機溶媒を使用してもよい。このような有機溶媒の具体例としては、アルコール類、ケトン類、芳香族類等が挙げられる。またアルコール類の具体例としては、メタノール、エタノール、プロピルアルコール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、グリセリン等が挙げられる。ケトン類の具体例としては、アセトン、メチルエチルケトン等が挙げられる。芳香族類の具体例としては、トルエン、キシレン等が挙げられる。 Water is generally used as the reaction solvent for synthesizing the resole-type phenol resin, but an organic solvent may be used. Specific examples of such an organic solvent include alcohols, ketones, aromatics and the like. Specific examples of alcohols include methanol, ethanol, propyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, glycerin and the like. Specific examples of the ketones include acetone, methyl ethyl ketone and the like. Specific examples of aromatics include toluene, xylene and the like.
　本実施形態のフェノール樹脂組成物シートにおいて、レゾール型フェノール樹脂の含有量は、フェノール樹脂組成物シート全体に対して、５０質量％以上９５質量％以下であり、好ましくは、６０質量％以上９５％質量％以下であり、より好ましくは、７０質量％以上９０質量％以下である。レゾール型フェノール樹脂の含有量を上記上限値以下とすることにより、得られるフェノール樹脂組成物シートの溶融時の粘度を低く抑えることができ、よって繊維基材に対する含浸性を向上することができる。また、レゾール型フェノール樹脂の含有量を上記下限値以上とすることにより、得られるフェノール樹脂組成物シートは、湿式摩擦材として使用するのに十分な耐熱性および耐久性を備える。さらにレゾール型フェノール樹脂の含有量を上記下限値以上とすることにより、得られるフェノール樹脂組成物シートの残炭率を高く維持することができ、よって当該シートを用いて製造される湿式摩擦材は、耐熱性および機械的強度において優れる。 In the phenol resin composition sheet of the present embodiment, the content of the resole-type phenol resin is 50% by mass or more and 95% by mass or less, preferably 60% by mass or more and 95% by mass, based on the entire phenol resin composition sheet. It is 0% by mass or less, and more preferably 70% by mass or more and 90% by mass or less. By setting the content of the resol type phenol resin to the above upper limit value or less, the viscosity of the obtained phenol resin composition sheet at the time of melting can be suppressed to a low level, and thus the impregnation property to the fiber base material can be improved. Further, by setting the content of the resol type phenol resin to the above lower limit value or more, the obtained phenol resin composition sheet has sufficient heat resistance and durability for use as a wet friction material. Further, by setting the content of the resol type phenol resin to the above lower limit value or more, the residual carbon content of the obtained phenol resin composition sheet can be maintained high, and therefore, the wet friction material produced by using the sheet can be used. Excellent in heat resistance and mechanical strength.
（ポリビニルブチラール）
　本実施形態のフェノール樹脂組成物シートに用いられるポリビニルブチラールは、液状のレゾール型フェノール樹脂を固形化する作用を有し、シート形成材として働く。またポリビニルブチラールを用いることにより、得られるフェノール樹脂組成物シートに、可撓性を付与することができる。よって、本実施形態のフェノール樹脂組成物シートは、所望の寸法に切断したり、目的の用途に応じて所望の形状に打ち抜き加工したりすることができる。ポリビニルブチラールは、酸触媒の存在下、ポリビニルアルコールをアルデヒドによりブチラール化することにより得られる樹脂である。 (Polyvinyl butyral)
The polyvinyl butyral used in the phenol resin composition sheet of the present embodiment has an action of solidifying a liquid resol type phenol resin and acts as a sheet forming material. Further, by using polyvinyl butyral, flexibility can be imparted to the obtained phenol resin composition sheet. Therefore, the phenolic resin composition sheet of the present embodiment can be cut to a desired size or punched into a desired shape according to a desired application. Polyvinyl butyral is a resin obtained by converting polyvinyl alcohol to butyral with an aldehyde in the presence of an acid catalyst.
　ポリビニルブチラールの重量平均分子量は、取り扱い性等の観点から、好ましくは１．０×１０４～１．０×１０６であり、より好ましくは２．０×１０４～５．０×１０５であり、さらに好ましくは３．０×１０４～２．０×１０５である。なお、重量平均分子量は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）により測定されたポリスチレン換算によるものをいう。 The weight average molecular weight of the polyvinyl butyral, from the viewpoint of handling properties, preferably 1.0 × 10 4 ~ 1.0 × 10 6, more preferably 2.0 × 10 4 ~ 5.0 × 10 5 Yes, more preferably 3.0 × 10 4 to 2.0 × 10 5 . The weight average molecular weight is based on polystyrene conversion measured by gel permeation chromatography (GPC).
　ポリビニルブチラールの重合度は、２００～３０００の範囲が好ましい。重合度を２００以上とすることにより、得られるフェノール樹脂組成物シートの機械的強度を確保することができ、重合度を３０００以下とすることにより、得られるフェノール樹脂組成物シートが適度な可撓性を有し、取扱い性に優れたものとなり得る。 The degree of polymerization of polyvinyl butyral is preferably in the range of 200 to 3000. By setting the degree of polymerization to 200 or more, the mechanical strength of the obtained phenol resin composition sheet can be ensured, and by setting the degree of polymerization to 3000 or less, the obtained phenol resin composition sheet is appropriately flexible. It has a property and can be excellent in handleability.
　ポリビニルブチラールの含有量は、フェノール樹脂組成物全体に対し、たとえば、２質量％以上５０質量％以下であり、好ましくは、５質量％以上４０質量％以下であり、より好ましくは、１０質量％以上３０質量％以下である。ポリビニルブチラールの含有量を上記下限値以上とすることにより、得られるフェノール樹脂組成物シートは、シートの形状を維持するのに十分な強度および可撓性を有し、使用時に繊維基材上に配置される際の取り扱い性に優れる。また、ポリビニルブチラールの含有量を上記上限値以下とすることにより、得られるフェノール樹脂組成物シートの溶融時の粘度を低く抑えることができ、よって繊維基材に対する含浸性を向上することができる。またポリビニルブチラールの含有量を上記上限値以下とすることにより、得られるフェノール樹脂組成物シートは、湿式摩擦材として使用するのに十分な耐熱性および耐久性を備える。さらにポリビニルブチラールの含有量を上記上限値以下とすることにより、得られるフェノール樹脂組成物シートの残炭率を高く維持することができ、よって当該シートを用いて製造される湿式摩擦材は、耐熱性および機械的強度において優れる。 The content of polyvinyl butyral is, for example, 2% by mass or more and 50% by mass or less, preferably 5% by mass or more and 40% by mass or less, and more preferably 10% by mass or more, based on the entire phenol resin composition. It is 30% by mass or less. By setting the content of polyvinyl butyral to the above lower limit or more, the obtained phenol resin composition sheet has sufficient strength and flexibility to maintain the shape of the sheet, and is placed on the fiber substrate during use. Excellent handleability when placed. Further, by setting the content of polyvinyl butyral to the above upper limit value or less, the viscosity of the obtained phenol resin composition sheet at the time of melting can be suppressed to a low level, and thus the impregnation property to the fiber substrate can be improved. Further, by setting the content of polyvinyl butyral to the above upper limit value or less, the obtained phenol resin composition sheet has sufficient heat resistance and durability for use as a wet friction material. Further, by setting the content of polyvinyl butyral to the above upper limit or less, the residual carbon content of the obtained phenol resin composition sheet can be maintained high, and therefore, the wet friction material produced by using the sheet has heat resistance. Excellent in properties and mechanical strength.
（その他の成分）
　本実施形態のフェノール樹脂組成物シートは、レゾルシン類をさらに含んでもよい。レゾルシン類を含むことにより、フェノール樹脂組成物シートの硬化速度を向上することができる。レゾルシン類の具体例としては、レゾルシン、２－メチルレゾルシン、５－メチルレゾルシン、２，５－ジメチルレゾルシン等のメチルレゾルシン類、４－エチルレゾルシン、４－クロロレゾルシン、２－ニトロレゾルシン、４－ブロモレゾルシン、４－ｎ－ヘキシルレゾルシンなどが挙げられる。これらは、単独で使用してもよいし、２種以上を混合して使用してもよい。中でも、製造コストとシート成形性の観点から、レゾルシン、またはメチルレゾルシンを用いることが好ましい。 (Other ingredients)
The phenolic resin composition sheet of the present embodiment may further contain resorcins. By containing resorcins, the curing rate of the phenol resin composition sheet can be improved. Specific examples of resorcins include methyl resorcins such as resorcin, 2-methylresorcin, 5-methylresorcin, and 2,5-dimethylresorcin, 4-ethylresorcin, 4-chlororesorcin, 2-nitroresorcin, and 4-bromo. Resorcin, 4-n-hexyl resorcin and the like can be mentioned. These may be used alone or in combination of two or more. Above all, it is preferable to use resorcin or methylresorcin from the viewpoint of manufacturing cost and sheet formability.
　本実施形態のフェノール樹脂組成物シートは、上記成分に加え、本発明の効果を損なわない範囲で、ニトリルブタジエンゴムおよびスチレンブタジエンゴム等のエラストマー、界面活性剤、難燃剤、酸化防止剤、着色剤、シランカップリング剤等の添加剤を含んでもよい。 In addition to the above components, the phenolic resin composition sheet of the present embodiment contains elastomers such as nitrile butadiene rubber and styrene butadiene rubber, surfactants, flame retardants, antioxidants, and colorants as long as the effects of the present invention are not impaired. , Additives such as silane coupling agents may be included.
（フェノール樹脂組成物シートの作製）
　本実施形態のフェノール樹脂組成物シートは、上記成分を有機溶剤に溶解して得られる液状またはワニス状のフェノール樹脂組成物を、基材シート等に塗布し、加熱処理により有機溶剤を除去してシート状に成形し、その後加熱処理によりＢステージ状態（半硬化状態）にすることにより作製される。フェノール樹脂組成物シートの厚みは、５μｍ以上２００μｍ以下であることが好ましい。フェノール樹脂組成物シートは、幅１０ｍｍ以上１００ｍｍ以下の範囲のテープ状、または幅１０ｃｍ以上２００ｃｍ以下の範囲のシート状とすることができる。 (Preparation of phenol resin composition sheet)
In the phenol resin composition sheet of the present embodiment, a liquid or varnish-like phenol resin composition obtained by dissolving the above components in an organic solvent is applied to a base sheet or the like, and the organic solvent is removed by heat treatment. It is produced by forming it into a sheet and then heat-treating it to a B stage state (semi-cured state). The thickness of the phenol resin composition sheet is preferably 5 μm or more and 200 μm or less. The phenol resin composition sheet can be in the form of a tape having a width of 10 mm or more and 100 mm or less, or a sheet having a width of 10 cm or more and 200 cm or less.
　ワニス状のフェノール樹脂組成物に用いられる有機溶剤としては、メタノール、エタノール、イソプロパノール、ブタノールなどのアルコール系有機溶媒、アセトン、メチルエチルケトン、メチルイソブチルケトンなどのケトン系有機溶媒、トルエン、エチルベンゼンなどの芳香族炭化水素溶媒およびこれらの混合物が挙げられる。中でも、メタノールが好ましく用いられる。 Examples of the organic solvent used in the varnish-like phenol resin composition include alcohol-based organic solvents such as methanol, ethanol, isopropanol and butanol, ketone-based organic solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and aromatics such as toluene and ethyl benzene. Examples include hydrocarbon solvents and mixtures thereof. Of these, methanol is preferably used.
　ワニス状のフェノール樹脂組成物は、上記成分を有機溶剤中で混練して作製される。混練は、通常の攪拌機、三本ロール、ボールミル等の分散機を適宜組み合わせて行うことができる。 The varnish-like phenol resin composition is prepared by kneading the above components in an organic solvent. The kneading can be carried out by appropriately combining a normal stirrer, a three-roll, a disperser such as a ball mill.
　ワニス状のフェノール樹脂組成物をシート状に成形する工程は、基材シートに、ワニス状フェノール樹脂組成物を塗布し、加熱乾燥して有機溶剤を除去して、フェノール樹脂組成物層を形成させることにより行われる。加熱乾燥の条件は、使用された有機溶剤が揮発する条件であればよく、例えば、５０℃～１５０℃の温度で、１分～９０分間の時間で行われる。 In the step of forming the varnish-like phenol resin composition into a sheet, the varnish-like phenol resin composition is applied to the base sheet and dried by heating to remove the organic solvent to form the phenol resin composition layer. It is done by. The heat-drying condition may be any condition as long as the organic solvent used is volatilized, and is performed, for example, at a temperature of 50 ° C. to 150 ° C. for a time of 1 minute to 90 minutes.
　上述のようにして得られたフェノール樹脂組成物層は、さらに加熱処理を行うことにより、半硬化（Ｂステージ）状態とされる。半硬化状態とするための加熱処理としては、１００～２００℃の温度で、１分～６０分の時間の条件を用いることができる。 The phenolic resin composition layer obtained as described above is further heat-treated to be in a semi-cured (B stage) state. As the heat treatment for making the semi-cured state, a condition of a temperature of 100 to 200 ° C. and a time of 1 minute to 60 minutes can be used.
　シート状基材としては、上述の加熱乾燥条件に耐え得るものであれば特に制限されず、例えば、ポリエステル系フィルム、ポリプロピレン系フィルム、ポリイミド系フィルム、ポリアミド系フィルム、ポリスルホン系フィルム、ポリーエーテルケトン系フィルム等が使用される。これらのシート状基材は、その表面が離型剤で処理されていてもよい。基材シートは、フェノール樹脂組成物層が形成された後に除去してもよい。また、このようにして得られたフェノール樹脂組成物シートは、基材シートと対向した面とは反対の面に、剥離フィルムが設けられた、剥離フィルム付フェノール樹脂組成物シートとして提供されてもよい。剥離フィルムとしては、基材シートと同様のものを用いることができる。 The sheet-like substrate is not particularly limited as long as it can withstand the above-mentioned heat-drying conditions, and is, for example, a polyester-based film, a polypropylene-based film, a polyimide-based film, a polyamide-based film, a polysulfone-based film, or a polyetherketone-based film. Film or the like is used. The surface of these sheet-like substrates may be treated with a mold release agent. The base sheet may be removed after the phenolic resin composition layer is formed. Further, the phenol resin composition sheet thus obtained may be provided as a phenol resin composition sheet with a release film, in which a release film is provided on a surface opposite to the surface facing the base sheet. good. As the release film, the same one as the base sheet can be used.
　本実施形態のフェノール樹脂組成物シートの最低溶融粘度は、例えば、５０００Ｐａ・ｓ以下であり、好ましくは、４０００Ｐａ・ｓ以下であり、より好ましくは、３０００Ｐａ・ｓ以下である。最低溶融粘度は、用いるフェノール樹脂の種類、およびポリビニルブチラールの配合量を上述の範囲とすることにより調整することができる。フェノール樹脂組成物シートの最低溶融粘度の下限値は、例えば、２００Ｐａ・ｓ以上である。上記範囲の最低溶融粘度であれば、繊維基材内部まで容易に含浸させることができ、室温で液状の含浸用フェノール樹脂組成物を用いた場合と同程度の含浸性とすることができる。 The minimum melt viscosity of the phenolic resin composition sheet of the present embodiment is, for example, 5000 Pa · s or less, preferably 4000 Pa · s or less, and more preferably 3000 Pa · s or less. The minimum melt viscosity can be adjusted by setting the type of phenol resin used and the blending amount of polyvinyl butyral within the above ranges. The lower limit of the minimum melt viscosity of the phenolic resin composition sheet is, for example, 200 Pa · s or more. If the minimum melt viscosity is in the above range, the inside of the fiber base material can be easily impregnated, and the impregnation property can be the same as when the liquid impregnating phenol resin composition is used at room temperature.
　ここで、フェノール樹脂組成物シートの最低溶融粘度とは、このフェノール樹脂組成物シートが加熱により溶融された際に、フェノール樹脂組成物が呈する最低の粘度をいう。詳細には、一定の昇温速度でフェノール樹脂組成物シートを加熱して樹脂を溶融させると、初期の段階は溶融粘度が温度上昇とともに低下し、その後、ある程度を超えると温度上昇とともに溶融粘度が上昇する。最低溶融粘度とは、斯かる極小点の溶融粘度をいう。樹脂組成物層の最低溶融粘度は、動的粘弾性法により測定することができる。 Here, the minimum melt viscosity of the phenol resin composition sheet means the minimum viscosity exhibited by the phenol resin composition when the phenol resin composition sheet is melted by heating. Specifically, when the phenol resin composition sheet is heated at a constant temperature rise rate to melt the resin, the melt viscosity decreases with increasing temperature in the initial stage, and then, when the temperature exceeds a certain level, the melt viscosity increases with temperature increase. To rise. The minimum melt viscosity means the melt viscosity at such a minimum point. The minimum melt viscosity of the resin composition layer can be measured by the dynamic viscoelastic method.
　本実施形態のフェノール樹脂組成物シートは、残炭率が、たとえば、３０質量％以上であり、好ましくは、３５質量％以上であり、より好ましくは、４０質量％以上である。フェノール樹脂組成物シートの残炭率の上限値は特に制限されないが、例えば、８０質量％以下である。本明細書中において、フェノール樹脂組成物シートの残炭率は、ＪＩＳ　Ｋ６９１０に準じて測定される、８００℃の温度における残炭率である。本実施形態のフェノール樹脂組成物シートは、上述のレゾール型フェノール樹脂を、上述の配合量で含むことにより、３０質量％以上の残炭率を有する。このようなフェノール樹脂組成物シートは、耐熱性に優れ、よってこれを用いて製造される湿式摩擦材は、優れた耐熱性を有する。 The phenolic resin composition sheet of the present embodiment has a residual carbon content of, for example, 30% by mass or more, preferably 35% by mass or more, and more preferably 40% by mass or more. The upper limit of the residual carbon content of the phenol resin composition sheet is not particularly limited, but is, for example, 80% by mass or less. In the present specification, the residual coal ratio of the phenol resin composition sheet is the residual carbon ratio at a temperature of 800 ° C. measured according to JIS K6910. The phenol resin composition sheet of the present embodiment has a residual carbon content of 30% by mass or more by containing the above-mentioned resole-type phenol resin in the above-mentioned blending amount. Such a phenol resin composition sheet has excellent heat resistance, and therefore the wet friction material produced by using the same has excellent heat resistance.
（フェノール樹脂組成物シートの用途）
　本実施形態のフェノール樹脂組成物シートは、フェノール樹脂組成物に含浸された繊維基材（前駆体シート）を硬化、焼成（炭化）処理することにより作製される湿式摩擦材に用いられる。
　一実施形態において、フェノール樹脂組成物に含浸された繊維基材（前駆体シート）は、繊維基材と、繊維基材に含浸されたＢステージ状のフェノール樹脂組成物とから構成される、Ｂステージ化フェノール樹脂複合シートとして提供される。このＢステージ化フェノール樹脂複合シートは、以下の工程により製造される。
（Ａ１）シート状基材（繊維基材）を準備する工程；
（Ａ２）シート状基材の少なくとも一方の面上に本実施形態のフェノール樹脂組成物シートを積層する工程；
（Ａ３）このフェノール樹脂組成物シートを加熱することによりフェノール樹脂組成物シートを溶融して液状化し、液状化フェノール樹脂組成物をシート状基材に含浸させる工程、樹脂含浸シート（Ｂステージ化フェノール樹脂複合シート）を作製する工程。 (Use of phenol resin composition sheet)
The phenol resin composition sheet of the present embodiment is used as a wet friction material produced by curing and firing (carbonizing) a fiber base material (precursor sheet) impregnated with the phenol resin composition.
In one embodiment, the fiber base material (precursor sheet) impregnated with the phenol resin composition is composed of a fiber base material and a B-stage-like phenol resin composition impregnated with the fiber base material. Provided as a staged phenolic resin composite sheet. This B-staged phenol resin composite sheet is produced by the following steps.
(A1) Step of preparing sheet-like base material (fiber base material);
(A2) A step of laminating the phenol resin composition sheet of the present embodiment on at least one surface of the sheet-like substrate;
(A3) A step of heating the phenol resin composition sheet to melt and liquefy the phenol resin composition sheet and impregnate the sheet-like substrate with the liquefied phenol resin composition, a resin-impregnated sheet (B-staged phenol). A process of producing a resin composite sheet).
　上記工程（Ａ１）のシート状基材を準備する工程は、炭素繊維またはアラミド繊維を抄紙し、シート状の基材を作製する工程である。シート状基材は市販の製品を使用してもよい。シート状基材は湿式摩擦材となる繊維基材（抄造体）であり、これには摩擦を制御する摩擦調整剤等の添加剤を添加してもよい。 The step of preparing the sheet-shaped base material in the above step (A1) is a step of making a sheet-shaped base material by making paper from carbon fibers or aramid fibers. A commercially available product may be used as the sheet-like substrate. The sheet-like base material is a fiber base material (paper machine) to be a wet friction material, and an additive such as a friction modifier for controlling friction may be added to the fiber base material (papermaking body).
　上記工程（Ａ２）は、（Ａ１）で準備したシート状基材の一方の面または両面に、本実施形態のフェノール樹脂組成物シートを積層した後、これを加熱により溶融して、シート状基材に含浸させる工程である。本実施形態のフェノール樹脂組成物シートは、シート状であるため、シート状基材に積層する工程が容易であり、フェノール樹脂組成物をシート状基材に含浸させる工程を、液状のフェノール樹脂を繊維基材に含浸させる手法に比べて、比較的簡単に実施することができる。 In the above step (A2), the phenol resin composition sheet of the present embodiment is laminated on one surface or both sides of the sheet-like substrate prepared in (A1), and then melted by heating to form a sheet-like group. This is the process of impregnating the material. Since the phenol resin composition sheet of the present embodiment is in the form of a sheet, the step of laminating on the sheet-like substrate is easy, and the step of impregnating the sheet-like substrate with the phenol resin composition is carried out by using a liquid phenol resin. It can be carried out relatively easily as compared with the method of impregnating the fiber base material.
　工程（Ａ２）において、フェノール樹脂組成物シートが積層されたシート状基材を加熱する工程は、加圧下で実施されることが好ましい。これにより、溶融したフェノール樹脂組成物は、シート状基材に含浸し易くなる。加熱、加圧の条件は、例えば、６０℃～１５０℃の温度、１ＭＰａ～５０ＭＰａの圧力が用いられる。 In the step (A2), the step of heating the sheet-like base material on which the phenol resin composition sheet is laminated is preferably carried out under pressure. As a result, the molten phenol resin composition is easily impregnated into the sheet-like substrate. As the heating and pressurizing conditions, for example, a temperature of 60 ° C. to 150 ° C. and a pressure of 1 MPa to 50 MPa are used.
　本実施形態のフェノール樹脂組成物シートは、有機溶剤をほとんどまたは全く含まないため、加熱時に溶剤の揮発が生じない。そのため、良好な作業環境が保障される。また、シート状のフェノール樹脂組成物を繊維基材上に配置する工程は一工程で実施できるため、作業効率が改善される。 Since the phenol resin composition sheet of the present embodiment contains almost or no organic solvent, the solvent does not volatilize during heating. Therefore, a good working environment is guaranteed. Further, since the step of arranging the sheet-shaped phenol resin composition on the fiber base material can be carried out in one step, the work efficiency is improved.
　本実施形態のフェノール樹脂組成物シートは、シート状基材上に配置される前に、シート状基材の寸法および形状と一致するように切り抜き加工してもよい。また、本実施形態のフェノール樹脂組成物シートは、所望に応じて、シート状基材上に１シートのみ配置してもよいし、２シート以上の複数を配置してもよい。 The phenolic resin composition sheet of the present embodiment may be cut out so as to match the dimensions and shape of the sheet-like substrate before being placed on the sheet-like substrate. Further, as the phenol resin composition sheet of the present embodiment, only one sheet may be arranged on the sheet-like substrate, or a plurality of two or more sheets may be arranged, if desired.
　一実施形態において、フェノール樹脂組成物に含浸された繊維基材は、繊維基材と、硬化されたフェノール樹脂組成物とから構成される、硬化フェノール樹脂複合シートとして提供される。硬化フェノール樹脂複合シートは、以下の工程により製造することができる。
（Ａ４）上記（Ａ３）で得られたＢステージ化フェノール樹脂複合シートを加熱処理して、Ｂステージ状態のフェノール樹脂組成物を完全硬化させる工程。 In one embodiment, the fiber base material impregnated with the phenol resin composition is provided as a cured phenol resin composite sheet composed of the fiber base material and the cured phenol resin composition. The cured phenol resin composite sheet can be produced by the following steps.
(A4) A step of heat-treating the B-staged phenolic resin composite sheet obtained in (A3) above to completely cure the B-staged phenolic resin composition.
　上記工程（Ａ４）のフェノール樹脂組成物を完全硬化させる工程は、例えば、１００℃～２００℃の温度下で、３分～３時間の時間、加熱することにより実施することができる。 The step of completely curing the phenol resin composition in the above step (A4) can be carried out, for example, by heating at a temperature of 100 ° C. to 200 ° C. for 3 minutes to 3 hours.
　一実施形態において、フェノール樹脂組成物に含浸された繊維基材は、繊維基材と、炭素化されたフェノール樹脂組成物とから構成される、炭素化フェノール樹脂複合シートとして提供される。炭素化フェノール樹脂複合シートは、以下の工程により製造することができる。
（Ａ５）上記（Ａ４）で得られた硬化フェノール樹脂複合シートを加熱処理して、硬化フェノール樹脂組成物を炭素化する工程。 In one embodiment, the fiber base material impregnated with the phenol resin composition is provided as a carbonized phenol resin composite sheet composed of the fiber base material and the carbonized phenol resin composition. The carbonized phenol resin composite sheet can be produced by the following steps.
(A5) A step of heat-treating the cured phenol resin composite sheet obtained in (A4) above to carbonize the cured phenol resin composition.
　上記工程（Ａ５）のフェノール樹脂組成物を炭素化する工程は、例えば、３５０℃～２０００℃の温度下で、１時間～８時間の時間、加熱することにより実施することができる。 The step of carbonizing the phenolic resin composition in the above step (A5) can be carried out, for example, by heating at a temperature of 350 ° C. to 2000 ° C. for 1 hour to 8 hours.
　本実施形態の炭素化フェノール樹脂複合シートは、湿式摩擦材として使用することができる。 The carbonized phenol resin composite sheet of this embodiment can be used as a wet friction material.
　以上、本発明の実施形態について述べたが、これらは本発明の例示であり、上記以外の様々な構成を採用することもできる。 Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.
　以下、本発明を、実施例および比較例により説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
（実施例１）
　撹拌装置、還流冷却器及び温度計を備えた反応装置に、フェノール（１００重量部）、３７％ホルマリン水溶液（１５１重量部）（Ｆ／Ｐモル比＝１．７）、トリエチルアミン５重量部を添加し、還流条件下で４０分間反応させた。その後、９１ｋＰａの減圧条件下で脱水を行いながら系内の温度が７０℃に達したところでメタノール（４０重量部）を加えて、８０℃で２時間反応させ、レゾール型フェノール樹脂を得た。
　これに、メタノール（１２０重量部）、ポリビニルブチラール樹脂（計算分子量４０，０００、積水化学工業製、エスレックＢＭ－１）（３０重量部）を加えて溶解させて混合し、ポリビニルブチラール変性フェノール樹脂ワニスを得た。このワニスを、バーコーターを用いてｗｅｔ膜厚１００μｍで塗工した後、８０℃の乾燥機で１５分乾燥させることで、レゾール型フェノール樹脂７５質量％、ポリビニルブチラール２０質量％を含有するフェノール樹脂組成物シート１を得た。 (Example 1)
To a reaction device equipped with a stirrer, a reflux condenser and a thermometer, phenol (100 parts by weight), 37% formalin aqueous solution (151 parts by weight) (F / P molar ratio = 1.7), and 5 parts by weight of triethylamine were added. Then, the reaction was carried out under reflux conditions for 40 minutes. Then, while dehydrating under a reduced pressure condition of 91 kPa, methanol (40 parts by weight) was added when the temperature in the system reached 70 ° C., and the mixture was reacted at 80 ° C. for 2 hours to obtain a resol type phenol resin.
To this, methanol (120 parts by weight) and polyvinyl butyral resin (calculated molecular weight 40,000, manufactured by Sekisui Chemical Co., Ltd., Eslek BM-1) (30 parts by weight) were added, dissolved and mixed, and the polyvinyl butyral-modified phenol resin varnish was mixed. Got This varnish is coated with a bar coater to a wet thickness of 100 μm and then dried in a dryer at 80 ° C. for 15 minutes to contain 75% by mass of resole-type phenolic resin and 20% by mass of polyvinyl butyral. The composition sheet 1 was obtained.
（実施例２）
　実施例１におけるポリビニルブチラール樹脂（積水化学工業製、エスレックＢＭ－１）を、積水化学工業製ポリビニルブチラール樹脂エスレックＢＨ－３（計算分子量１１０，０００）に変えた以外は実施例１と同様の方法を用いて、レゾール型フェノール樹脂７５％、ポリビニルブチラール２０％を含有するフェノール樹脂組成物シート２を得た。 (Example 2)
The same method as in Example 1 except that the polyvinyl butyral resin (manufactured by Sekisui Chemical Co., Ltd., Eslek BM-1) in Example 1 was changed to the polyvinyl butyral resin Eslek BH-3 (calculated molecular weight 110,000) manufactured by Sekisui Chemical Co., Ltd. Was used to obtain a phenol resin composition sheet 2 containing 75% of resole-type phenol resin and 20% of polyvinyl butyral.
（比較例１）
　撹拌装置、還流冷却器及び温度計を備えた反応装置に、フェノール（１００重量部）、３７％ホルマリン水溶液（１５１重量部）（Ｆ／Ｐモル比＝１．７）、トリエチルアミン（５重量部）を添加し、還流条件下で４０分間反応させた。その後、９１ｋＰａの減圧条件下で脱水を行いながら系内の温度が７０℃に達したところでメタノール（４０重量部）を加えて、８０℃で２時間反応させ、レゾール型フェノール樹脂を得た。
　これに、ポリビニルブチラール樹脂（積水化学工業製、エスレックＢＨ－３）の８０％メタノール溶液、１１０重量部を加えて溶解させて混合し、ポリビニルブチラール変性フェノール樹脂ワニスを得た。このワニスを、バーコーターを用いてｗｅｔ膜厚１００μｍで塗工した後、８０℃の乾燥機で１５分乾燥させることで、レゾール型フェノール樹脂３５質量％、ポリビニルブチラール６０質量％を含有するフェノール樹脂組成物シート３を得た。 (Comparative Example 1)
In a reaction device equipped with a stirrer, a reflux condenser and a thermometer, phenol (100 parts by weight), 37% formalin aqueous solution (151 parts by weight) (F / P molar ratio = 1.7), triethylamine (5 parts by weight). Was added and reacted under reflux conditions for 40 minutes. Then, while dehydrating under a reduced pressure condition of 91 kPa, methanol (40 parts by weight) was added when the temperature in the system reached 70 ° C., and the mixture was reacted at 80 ° C. for 2 hours to obtain a resol type phenol resin.
To this, 110 parts by weight of an 80% methanol solution of polyvinyl butyral resin (manufactured by Sekisui Chemical Co., Ltd., Eslek BH-3) was added, dissolved and mixed to obtain a polyvinyl butyral-modified phenolic resin varnish. This varnish is coated with a bar coater to a wet thickness of 100 μm and then dried in a dryer at 80 ° C. for 15 minutes to contain 35% by mass of resole-type phenolic resin and 60% by mass of polyvinyl butyral. The composition sheet 3 was obtained.
（比較例２）
　日東シンコー株式会社製のエポキシ樹脂シートを使用した。 (Comparative Example 2)
An epoxy resin sheet manufactured by Nitto Shinko Co., Ltd. was used.
（比較例３）
　ソマール株式会社製のアクリルポリマーシートを使用した。 (Comparative Example 3)
An acrylic polymer sheet manufactured by SOMAR Corporation was used.
（参考例１）
　撹拌装置、還流冷却器及び温度計を備えた反応装置に、フェノール（１００重量部）、３７％ホルマリン水溶液（１５１重量部）（Ｆ／Ｐモル比＝１．７）、トリエチルアミン５重量部を添加し、還流条件下で４０分間反応させた。その後、９１ｋＰａの減圧条件下で脱水を行いながら系内の温度が７０℃に達したところでメタノール（４０重量部）を加えて、８０℃で２時間反応させ、レゾール型フェノール樹脂を得た。
　これにメタノール（１２０重量部）、ポリビニルブチラール樹脂（３０重量部）を加えて溶解させて混合し、レゾール型フェノール樹脂３０質量％、ポリビニルブチラール樹脂２０質量％、メタノール５０質量％を含有する液状フェノール樹脂組成物を得た。 (Reference example 1)
To a reaction device equipped with a stirrer, a reflux condenser and a thermometer, phenol (100 parts by weight), 37% formalin aqueous solution (151 parts by weight) (F / P molar ratio = 1.7), and 5 parts by weight of triethylamine were added. Then, the reaction was carried out under reflux conditions for 40 minutes. Then, while dehydrating under a reduced pressure condition of 91 kPa, methanol (40 parts by weight) was added when the temperature in the system reached 70 ° C., and the mixture was reacted at 80 ° C. for 2 hours to obtain a resol type phenol resin.
Methanol (120 parts by weight) and polyvinyl butyral resin (30 parts by weight) are added to this, dissolved and mixed, and liquid phenol containing 30% by mass of resol type phenol resin, 20% by mass of polyvinyl butyral resin and 50% by mass of methanol. A resin composition was obtained.
（物性評価）
　各実施例、比較例および参考例の樹脂シートまたは液状組成物について、以下の物性を測定し、樹脂シートの性能を評価した。結果を表１に示す。
　（最低溶融粘度）
　フェノール樹脂組成物シートまたは液状組成物をＡＲＥ－Ｇ２レオメーターにて、３０℃から２００℃まで１０℃／分の条件で昇温しながら複素粘度を測定し、最も低い粘度を最低溶融粘度とした。
　（残炭率）
　ＪＩＳ　Ｋ　６９１０に準じて、樹脂シートの残炭率を測定した。
　（引張強度）
　１２０ｍｍ×１０ｍｍ×厚さ１ｍｍのアラミド繊維基材上に樹脂シートを置き、熱プレス機で１００℃、３ＭＰａで３分間プレスすることで含浸させてから、１９０℃のオーブンで３０分間乾燥硬化させることで、硬化シートを試験片として得た。得られた硬化物を、引張強度試験機を用いて、ＪＩＳ　Ｋ６９１１に準じて、２５℃、引張速度１ｍｍ／分の条件で引張強度を測定した。
　（耐熱引張強度）
　上述の硬化物を、２５０℃の環境下に３０分載置した後、再度、引張強度試験機を用いて、ＪＩＳ　Ｋ６９１１に準じて、２５℃、引張速度１ｍｍ／分の条件で耐熱引張強度を測定した。
　（含浸性）
　１２０ｍｍ×１０ｍｍ×厚さ１ｍｍのアラミド繊維基材上に樹脂シートを置き、熱プレス機で１００℃、３ＭＰａで３分間プレスすることで含浸させてから、１９０℃のオーブンで３０分間乾燥硬化させることで、硬化シートを試験片として得た。含浸後、シートの下面まで樹脂が浸透していれば「○」、一部浸透していれば「△」、まったく浸透していなければ「×」として評価した。 (Evaluation of the physical properties)
The following physical properties were measured for the resin sheets or liquid compositions of each Example, Comparative Example and Reference Example, and the performance of the resin sheet was evaluated. The results are shown in Table 1.
(Minimum melt viscosity)
The complex viscosity was measured while raising the temperature of the phenolic resin composition sheet or liquid composition with an ARE-G2 rheometer at 10 ° C./min from 30 ° C. to 200 ° C., and the lowest viscosity was taken as the minimum melt viscosity. ..
(Residual coal rate)
The residual coal rate of the resin sheet was measured according to JIS K 6910.
(Tensile strength)
A resin sheet is placed on a 120 mm × 10 mm × 1 mm thick aramid fiber substrate, impregnated by pressing at 100 ° C. and 3 MPa for 3 minutes with a hot press machine, and then dried and cured in an oven at 190 ° C. for 30 minutes. Then, a cured sheet was obtained as a test piece. The obtained cured product was measured for tensile strength using a tensile strength tester under the conditions of 25 ° C. and a tensile speed of 1 mm / min according to JIS K6911.
(Heat-resistant tensile strength)
After the above-mentioned cured product was placed in an environment of 250 ° C. for 30 minutes, the heat-resistant tensile strength was again measured using a tensile strength tester under the conditions of 25 ° C. and a tensile speed of 1 mm / min according to JIS K6911. It was measured.
(Impregnability)
A resin sheet is placed on a 120 mm × 10 mm × 1 mm thick aramid fiber substrate, impregnated by pressing at 100 ° C. and 3 MPa for 3 minutes with a hot press machine, and then dried and cured in an oven at 190 ° C. for 30 minutes. Then, a cured sheet was obtained as a test piece. After impregnation, if the resin penetrated to the lower surface of the sheet, it was evaluated as "◯", if it partially penetrated, it was evaluated as "Δ", and if it did not penetrate at all, it was evaluated as "x".
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　実施例の樹脂シートは、繊維基材に対する含浸性が良好であるとともに、その硬化物の熱処理後の機械的強度においても優れており、摩擦材として好適に使用できる材料であった。 The resin sheet of the example had good impregnation property with respect to the fiber base material and also had excellent mechanical strength after heat treatment of the cured product, and was a material that could be suitably used as a friction material.
　この出願は、２０２０年５月２９日に出願された日本出願特願２０２０－０９４０５８号、２０２０年５月２９日に出願された日本出願特願２０２０－０９４０６４号、および、２０２０年５月２９日に出願された日本出願特願２０２０－０９４０７０号を基礎とする優先権を主張し、その開示の全てをここに取り込む。 This application was filed on May 29, 2020, Japanese Application No. 2020-094058, Japanese Application Japanese Patent Application No. 2020-094064, filed May 29, 2020, and May 29, 2020. Claims priorities on the basis of Japanese Patent Application No. 2020-90470 filed in, and incorporates all of its disclosures herein.

Claims (12)

  1. 　シート状基材の少なくとも一表面上にフェノール樹脂組成物の層を配置し、前記フェノール樹脂組成物の層を加熱することにより前記フェノール樹脂組成物を溶融して液状化し、前記基材に含浸させる工程に用いられる、フェノール樹脂組成物シートであって、
    　レゾール型フェノール樹脂と、
    　ポリビニルブチラールと、
    　を含み、
    　　前記レゾール型フェノール樹脂が、当該フェノール樹脂組成物シート全体に対して、５０質量％以上９５質量％以下の量であり、
    　Ｂステージ状であり、
    　シート状である、フェノール樹脂組成物シート。     A layer of the phenol resin composition is arranged on at least one surface of the sheet-like substrate, and the layer of the phenol resin composition is heated to melt and liquefy the phenol resin composition and impregnate the substrate. A phenolic resin composition sheet used in the process.
    Resol type phenol resin and
    Polyvinyl butyral and
    Including
    The amount of the resole-type phenol resin is 50% by mass or more and 95% by mass or less with respect to the entire phenol resin composition sheet.
    It is like a B stage,
    A sheet-like phenol resin composition sheet.
  2. 　前記ポリビニルブチラールが、当該フェノール樹脂組成物シート全体に対して、２質量％以上５０質量％以下の量である、請求項１に記載のフェノール樹脂組成物シート。 The phenol resin composition sheet according to claim 1, wherein the polyvinyl butyral is in an amount of 2% by mass or more and 50% by mass or less with respect to the entire phenol resin composition sheet.
  3. 　５μｍ以上２００μｍ以下の厚みを有する、請求項１または２に記載のフェノール樹脂組成物シート。 The phenolic resin composition sheet according to claim 1 or 2, which has a thickness of 5 μm or more and 200 μm or less.
  4. 　最低溶融粘度が、５０００Ｐａ・ｓ以下である、請求項１～３のいずれかに記載のフェノール樹脂組成物シート。 The phenolic resin composition sheet according to any one of claims 1 to 3, wherein the minimum melt viscosity is 5000 Pa · s or less.
  5. 　ＪＩＳ　Ｋ　６９１０に準じて測定される残炭率が、３０質量％以上である、請求項１～４のいずれかに記載のフェノール樹脂組成物シート。 The phenolic resin composition sheet according to any one of claims 1 to 4, wherein the residual coal ratio measured according to JIS K6910 is 30% by mass or more.
  6. 　剥離フィルムと、
    　前記剥離フィルムの一方の面に積層された、請求項１～５のいずれかに記載のフェノール樹脂組成物シートと、を備える剥離フィルム付フェノール樹脂組成物シート。     With the release film,
    The phenol resin composition sheet with a release film comprising the phenol resin composition sheet according to any one of claims 1 to 5, which is laminated on one surface of the release film.
  7. 　シート状基材の少なくとも一方の面上に、請求項１～５に記載のフェノール樹脂組成物シートを積層する工程と、
    　前記フェノール樹脂組成物シートを加熱することにより前記フェノール樹脂組成物シートを溶融して液状化し、前記液状化フェノール樹脂組成物を前記シート状基材に含浸させて、Ｂステージ化フェノール樹脂複合シートを得る工程を含む、
    　Ｂステージ化フェノール樹脂複合シートの製造方法。     The step of laminating the phenolic resin composition sheet according to claims 1 to 5 on at least one surface of the sheet-like substrate, and
    By heating the phenol resin composition sheet, the phenol resin composition sheet is melted and liquefied, and the sheet-like substrate is impregnated with the liquefied phenol resin composition to obtain a B-staged phenol resin composite sheet. Including the process of obtaining,
    A method for producing a B-staged phenolic resin composite sheet.
  8. 　前記シート状基材が、炭素繊維、またはアラミド繊維からなる繊維基材である、請求項７に記載のＢステージ化フェノール樹脂複合シートの製造方法。 The method for producing a B-staged phenolic resin composite sheet according to claim 7, wherein the sheet-like base material is a fiber base material made of carbon fiber or aramid fiber.
  9. 　シート状基材の少なくとも一方の面上に、請求項１～５のいずれかに記載のフェノール樹脂組成物シートを積層する工程と、
    　前記フェノール樹脂組成物シートを加熱することにより前記フェノール樹脂組成物シートを溶融して液状化し、前記液状化フェノール樹脂組成物を前記シート状基材に含浸させて、Ｂステージ化フェノール樹脂複合シートを得る工程と、
    　前記Ｂステージ化フェノール樹脂複合シートを加熱して、前記フェノール樹脂組成物を完全硬化させて、硬化フェノール樹脂複合シートを得る工程と、
    　を含む、硬化フェノール樹脂複合シートの製造方法。     The step of laminating the phenolic resin composition sheet according to any one of claims 1 to 5 on at least one surface of the sheet-like substrate,
    By heating the phenol resin composition sheet, the phenol resin composition sheet is melted and liquefied, and the sheet-like substrate is impregnated with the liquefied phenol resin composition to obtain a B-staged phenol resin composite sheet. The process of obtaining and
    A step of heating the B-staged phenol resin composite sheet to completely cure the phenol resin composition to obtain a cured phenol resin composite sheet.
    A method for producing a cured phenol resin composite sheet, which comprises.
  10. 　前記シート状基材が、炭素繊維、またはアラミド繊維からなる繊維基材である、請求項９に記載の硬化フェノール樹脂複合シートの製造方法。 The method for producing a cured phenol resin composite sheet according to claim 9, wherein the sheet-like base material is a fiber base material made of carbon fiber or aramid fiber.
  11. 　シート状基材の少なくとも一方の面上に、請求項１～５のいずれかに記載のフェノール樹脂組成物シートを積層する工程と、
    　前記フェノール樹脂組成物シートを加熱することにより前記フェノール樹脂組成物シートを溶融して液状化し、前記液状化フェノール樹脂組成物を前記シート状基材に含浸させて、Ｂステージ化フェノール樹脂複合シートを得る工程と、
    　前記Ｂステージ化フェノール樹脂複合シートを加熱して、前記フェノール樹脂組成物を完全硬化させて、硬化フェノール樹脂複合シートを得る工程と、
    　前記硬化フェノール樹脂複合シートを加熱して、前記フェノール樹脂組成物を炭素化して、炭素化フェノール樹脂複合シートを得る工程と、
    　を含む、炭素化フェノール樹脂複合シートの製造方法。     The step of laminating the phenolic resin composition sheet according to any one of claims 1 to 5 on at least one surface of the sheet-like substrate,
    By heating the phenol resin composition sheet, the phenol resin composition sheet is melted and liquefied, and the sheet-like substrate is impregnated with the liquefied phenol resin composition to obtain a B-staged phenol resin composite sheet. The process of obtaining and
    A step of heating the B-staged phenol resin composite sheet to completely cure the phenol resin composition to obtain a cured phenol resin composite sheet.
    A step of heating the cured phenol resin composite sheet to carbonize the phenol resin composition to obtain a carbonized phenol resin composite sheet.
    A method for producing a carbonized phenol resin composite sheet, which comprises.
  12. 　前記シート状基材が、炭素繊維、またはアラミド繊維からなる繊維基材である、請求項１１に記載の炭素化フェノール樹脂複合シートの製造方法。 The method for producing a carbonized phenol resin composite sheet according to claim 11, wherein the sheet-shaped base material is a fiber base material made of carbon fiber or aramid fiber.
PCT/JP2021/018179 2020-05-29 2021-05-13 Phenolic resin composition sheet, phenolic resin composition sheet with release film, method for producing b-staged phenolic resin composite sheet, method for producing cured phenolic resin composite sheet, and method for producing carbonized phenolic resin composite sheet WO2021241245A1 (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2020094064A JP2021187941A (en) 2020-05-29 2020-05-29 Resin composition sheet, resin composition sheet with release film, method for producing b-staged resin composite sheet, method for producing cured resin composite sheet, and method for producing carbonized resin composite sheet
JP2020094058A JP2021187940A (en) 2020-05-29 2020-05-29 Phenolic resin composition sheet, phenolic resin composition sheet with release film, method for producing b-staged phenolic resin composite sheet, method for producing cured phenolic resin composite sheet, and method for producing carbonized phenolic resin composite sheet
JP2020-094058 2020-05-29
JP2020-094070 2020-05-29
JP2020094070A JP2021187942A (en) 2020-05-29 2020-05-29 Phenolic resin composition sheet, phenolic resin composition sheet with release film, method for producing b-staged phenolic resin composite sheet, method for producing cured phenolic resin composite sheet, and method for producing carbonized phenolic resin composite sheet
JP2020-094064 2020-05-29

Publications (1)

Publication Number Publication Date
WO2021241245A1 true WO2021241245A1 (en) 2021-12-02

Family

ID=78745275

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/018179 WO2021241245A1 (en) 2020-05-29 2021-05-13 Phenolic resin composition sheet, phenolic resin composition sheet with release film, method for producing b-staged phenolic resin composite sheet, method for producing cured phenolic resin composite sheet, and method for producing carbonized phenolic resin composite sheet

Country Status (2)

Country Link
TW (1) TW202212468A (en)
WO (1) WO2021241245A1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08151460A (en) * 1994-11-29 1996-06-11 Matsushita Electric Works Ltd Sheetlike molding material
WO2018030162A1 (en) * 2016-08-09 2018-02-15 住友ベークライト株式会社 Resin composition for friction materials and wet paper friction material
JP2020063362A (en) * 2018-10-17 2020-04-23 住友ベークライト株式会社 Adhesive composition for wet friction material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08151460A (en) * 1994-11-29 1996-06-11 Matsushita Electric Works Ltd Sheetlike molding material
WO2018030162A1 (en) * 2016-08-09 2018-02-15 住友ベークライト株式会社 Resin composition for friction materials and wet paper friction material
JP2020063362A (en) * 2018-10-17 2020-04-23 住友ベークライト株式会社 Adhesive composition for wet friction material

Also Published As

Publication number Publication date
TW202212468A (en) 2022-04-01

Similar Documents

Publication Publication Date Title
JP6259770B2 (en) Resin composition and precursor of carbon fiber reinforced composite material, carbon fiber reinforced composite material, and carbon fiber reinforced carbon material obtained using the same
WO2016159218A1 (en) Modified phenolic resole resin composition, method for producing same, and adhesive
US9862823B2 (en) Resin composition for wet friction material, phenolic resin for wet friction material and wet friction material
US10259902B2 (en) Resol phenolic resin for friction material, method for producing the same, adhesive for friction material, and wet friction plate
JP7172422B2 (en) Adhesive composition for wet friction material
WO2021241245A1 (en) Phenolic resin composition sheet, phenolic resin composition sheet with release film, method for producing b-staged phenolic resin composite sheet, method for producing cured phenolic resin composite sheet, and method for producing carbonized phenolic resin composite sheet
JP2021187940A (en) Phenolic resin composition sheet, phenolic resin composition sheet with release film, method for producing b-staged phenolic resin composite sheet, method for producing cured phenolic resin composite sheet, and method for producing carbonized phenolic resin composite sheet
JP2021187942A (en) Phenolic resin composition sheet, phenolic resin composition sheet with release film, method for producing b-staged phenolic resin composite sheet, method for producing cured phenolic resin composite sheet, and method for producing carbonized phenolic resin composite sheet
JP2021187941A (en) Resin composition sheet, resin composition sheet with release film, method for producing b-staged resin composite sheet, method for producing cured resin composite sheet, and method for producing carbonized resin composite sheet
JP2008189749A (en) Phenolic resin for wet type paper friction material, and wet type paper friction material
JP2010138273A (en) Phenolic resin composition for wet friction material and friction material
JP2020172582A (en) Adhesive composition for wet friction material and wet friction plate
JP2020063362A (en) Adhesive composition for wet friction material
JP2020063360A (en) Adhesive composition for wet friction material
JP7351439B1 (en) Adhesive composition for wet friction materials and wet friction plates
JP7168121B1 (en) resin composition
JP2021031651A (en) Thermosetting adhesive sheet for friction material and method for manufacturing friction member
JP2020063361A (en) Adhesive composition for wet friction material
JP7338809B1 (en) Phenolic resin composition and articles
CN114599757B (en) Adhesive composition for wet friction material
WO2023195481A1 (en) Adhesive composition for wet friction material, and wet friction plate
JP2021187919A (en) Phenol resin composition for wet friction material, wet friction material and method for producing the same
JP2021187918A (en) Phenol resin composition for wet friction material, wet friction material and method for producing the same
JP2019038945A (en) Phenolic resin for wet friction material, phenolic resin composition and wet friction material
JP2023153489A (en) Adhesive composition for wet friction material and wet friction plate

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21814265

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21814265

Country of ref document: EP

Kind code of ref document: A1